Process for making a two-cycle gasoline engine lubricant

ABSTRACT

A process to prepare a lubricating oil meeting JASO M345:2003 requirements, comprising: hydroisomerization dewaxing a feed to produce a base oil and blending the base oil with less than 5 wt % solvent and a detergent/dispersant additive package. A process for making lubricating oil, comprising blending together a pour point reduced base oil blend with a detergent/dispersant additive package, a smoke-suppression agent, optionally a pour point depressant, and optionally less than about 5 wt % hydrocarbon solvent, whereby a two-cycle gasoline engine lubricant is produced. A process to make a two-cycle gasoline engine lubricant, comprising preparing a pour point reducing blend component by isomerizing a feed, blending it with a light distillate base oil to produce a pour point reduced base oil blend, and blending the pour point reduced base oil blend with a detergent/dispersant additive package and less than 5 wt % solvent. A lubricating oil made by the process described herein.

FIELD OF THE INVENTION

This invention is directed to a process for making an improved two-cyclegasoline engine lubricant composition requiring reduced amounts ofhydrocarbon solvent.

BACKGROUND OF THE INVENTION

Two-cycle engines have three important advantages over four-cycleengines:

-   -   Two-cycle engines do not have valves, which simplifies their        construction and lowers their weight.

Two-cycle engines fire once every revolution, while four-cycle enginesfire once every other revolution. This gives two-cycle engines asignificant power boost.

Two-cycle engines can work in any orientation, which can be important insomething like a chainsaw. A standard four-cycle engine may haveproblems with oil flow unless it is upright, and solving this problemcan add complexity to the engine.

There are at least three potential disadvantages of two-cycle engines,including:

-   -   Two-cycle engines don't last nearly as long as four-cycle        engines. The lack of a dedicated lubrication system means that        the parts of a two-cycle engine wear a lot faster.    -   Two-cycle gasoline engine lubricant is expensive, and you need        about 4 ounces of it per gallon of gasoline. About a gallon of        lubricant would be consumed every 1,000 miles if you used a        two-cycle engine in an automobile.    -   Two-cycle engines produce a lot of pollution, including smoke        from the combustion of the two-cycle gasoline engine lubricant,        and leakage of the two-cycle gasoline engine lubricant out        through the exhaust port.

The majority of two-cycle gasoline engine lubricants are formulated withlow-boiling hydrocarbon solvent and SAE 40 mineral base oils. Othershave used ester base oils with no low-boiling solvent to reduce thehazard potential and minimize smoky emissions, however these lubricantsdo not have very good oxidation stability. Others have usedpolyalphaolefin base oils having improved low temperature properties.Polyalphaolefin and ester base oils are limited in supply and veryexpensive. Improved two-cycle gasoline engine lubricant compositions,comprising less expensive base oils, and meeting the requirements set bystandard setting organizations are desired. It is also desired thatthese lubricant compositions have reduced levels of hydrocarbon solvent,reduced engine wear, and reduced pollution. It is also desired thattwo-cycle gasoline engine lubricant compositions have good lowtemperature performance, good gasoline miscibility, and high oxidationstability. It is also desired that two-cycle gasoline engine lubricantcompositions have higher flash points and reduced flammability. It isalso desired that two-cycle gasoline engine lubricant compositions canbe made using polyethylene plastic, to reduce waste plasticenvironmental pollution.

SUMMARY OF THE INVENTION

The present invention provides a process to prepare a lubricating oil,comprising.

-   -   a. hydroisomerization dewaxing a substantially paraffinic wax        feed to produce a lubricating base oil; and    -   b. blending one or more fractions of the lubricating base oil        with:        -   i. less than about 5 wt % based on the total lubricating oil            composition of a hydrocarbon solvent having a maximum            boiling point less than 250 degrees C., and        -   ii. a detergent/dispersant additive package; wherein the            lubricating oil meets the requirements of JASO MA345:2003.

The present invention also provides a process for making a lubricatingoil, comprising:

-   -   a. blending together:        -   i. one or more fractions of base oil having a kinematic            viscosity at 100° C. between about 1.5 and about 3.5 mm²/s,            and        -   ii. a pour point reducing blend component, to produce a pour            point reduced base oil blend;    -   b. adding to the pour point reduced base oil blend:        -   i. a detergent/dispersant additive package;        -   ii. a smoke-suppression agent;        -   iii. optionally a pour point depressant; and        -   iv. optionally less than about 5 wt % hydrocarbon solvent            having a maximum boiling point less than 250 degrees C.;    -   whereby a two-cycle gasoline engine lubricant is produced.

The present invention also provides a process for making a two-cyclegasoline engine lubricant meeting the JASO M345:2003 requirements,comprising:

-   -   a. preparing a pour point reducing, blend component by        isomerizing a feed;    -   b. blending the pour point reducing blend component with        -   i. a distillate base oil having a kinematic viscosity at            100° C. between about 1.5 and about 3.5 mm²/s to produce a            pour point reduced base oil blend;    -   c. blending the pour point reduced base oil blend with:        -   i. a detergent/dispersant additive package; and        -   ii. less than 5 wt %, based on the total two-cycle gasoline            engine lubricant, of a hydrocarbon solvent having a maximum            boiling point less than 250 degrees C.;    -    in the proper proportions to yield the two-cycle gasoline        engine lubricant.

The present invention also provides a lubricating oil made by a process,comprising:

-   -   a. hydroisomerization dewaxing a substantially paraffinic wax        feed, whereby a lubricating base oil is produced; and    -   b. blending one or more fractions of the lubricating base oil        with:        -   i. less than about 5 wt % based on the total lubricating oil            composition of a hydrocarbon solvent having a maximum            boiling point less than 250 degrees C., and        -   ii. a detergent/dispersant additive package; whereby the            lubricating oil meets the requirements of JASO M345:2003.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 illustrates the plots of Kinematic Viscosity at 100° C. vs. NoackVolatility, in weight percent, providing the equations for calculationof the upper limits of wt % Noack Volatility of:

Noack Volatility Factor (1)=160−40(Kinematic Viscosity at 100° C.), and

Noack Volatility Factor (2)=900×(Kinematic Viscosity at 100°C.)^(−2.8)−15, wherein the Kinematic Viscosity at 100° C. is raised tothe power of −2.8 in the second equation.

DETAILED DESCRIPTION OF THE INVENTION

To operate a two-cycle gasoline engine the crankcase holds a mixture oftwo-cycle gasoline engine lubricant and fuel. In a two-cycle engine thecrankcase is serving as a pressurization chamber to force air/fuel intothe cylinder, so it can't hold high viscosity oil like what may be usedin a four-cycle engine. Instead, specialized two-cycle gasoline enginelubricant is mixed in with the fuel to lubricate the crankshaft,connecting rod and cylinder walls.

The recommended mix ratio of two-cycle gasoline engine lubricant andfuel are specified by the engine manufacturer. The fuels useful intwo-cycle gasoline engines are well known to those skilled in the artand usually contain a major portion of a normally liquid fuel such as ahydrocarbonaceous petroleum distillate fuel, e.g., spark ignition enginefuel as defined by ASTM D4814-07, or motor gasoline as defined by ASTMD439-89. Such fuels can also contain non-hydrocarbonaceous materialssuch as alcohols, ethers, organo nitro compounds and the like. Forexample, methanol, ethanol, diethyl ether, methylethyl ether, nitromethane and such fuels are within the scope of this invention as areliquid fuels derived from vegetable and mineral sources such as corn,switch grass, alpha shale and coal. Examples of such fuel mixtures arecombinations of gasoline and ethanol, diesel fuel and ether, gasolineand nitro methane, etc. In one embodiment the fuel is lead-freegasoline.

Two-cycle gasoline engine lubricants are used in admixture with fuels inamounts of about 20 to 250 parts by weight of fuel per 1 part by weightof lubricating oil, more typically about 30-100 parts by weight of fuelper 1 part by weight of lubricant.

Two-cycle gasoline engine lubricants must meet requirements set bystandards setting organizations, including Japanese Automobile StandardJASO M345:2003 and International Standard ISO 1373832000(E). Therequirements of these two standards are summarized in the table below.

TABLE I Classification Test Performance Parameter B C D Method KinematicViscosity at 100° C., mm²/s 6.5 6.5 6.5 ISO 3104 min. min. min. FlashPoint, ° C., Pensky-Martens 70 70 70 JIS K closed cup method min. min.min. 2265 Sulfated Ash, wt % 0.25 0.25 0.18 ISO 3987 max. max. max.Lubricity Index 95 95 95 JASO min. min. min. M340-92 Initial TorqueIndex 98 98 98 JASO min. min. min. M340-92 60-minute evaluation 85 95 —JASO Detergency Index min. min. M341-92 180-minute evaluation — — 125CEC L- min. 079-T-97 Piston-Skirt Deposits Index 85 90 — JASO min. min.M341-92 — — 95 CEC L- min. 079-T-97 Exhaust Smoke Index 45 85 85 JASOmin. min. min. M342-92 Exhaust-System Blocking Index 45 90 90 JASO min.min. min. M343-92

The indexes in the table above are determined by taking JATRE-1 oil ashaving a value of 100. Classification C applies to what is calledlow-smoke type oil that has superior exhaust smoke performance andexhaust system blocking tendency. Classification D is applied to oilswith better detergency that Classification C oils when the engine ishot.

Classification B, C and D oils in the ISO standard all have a sulfatedash content of 0.18 wt % maximum. Sulfated ash may be measured accordingto ISO 3987 or ASTM D874-00.

Additionally, it is desired that these lubricants have good lowtemperature fluidity when they are to be used in conditions where lowtemperatures are encountered. Low temperature fluidity is measured bydetermining the Brookfield Viscosity measured by ASTM D2983-04a atdefined temperatures of −10-25° C., and 40° C. “Good low temperaturefluidity” at one of the temperatures measured is defined in thisdisclosure as when the oil being tested has a Brookfield Viscosity ofabout 7500 mPa·s or less. For example, good low temperature fluidity at−10° C. means that the oil has a Brookfield Viscosity at −10° C. ofabout 7500 mPa·s or less; good low temperature fluidity at −25° C. meansthat the oil has a Brookfield Viscosity at −25° C. of about 7500 mPa·sor less; and good low temperature fluidity at 40° C. means that the oilhas a Brookfield Viscosity at −40° C. of about 7500 mPa·s or less.

Additionally, it is desired that these lubricants have passing resultsin the miscibility test by ASTM D4682-87(Reapproved 2002) attemperatures of −10° C. and/or −25° C.

The two-cycle gasoline engine lubricant compositions are particularlysuited as injector oils or at up to a 150:1 fuel to lubricant mix ratiowith an appropriate fuel such as gasoline in carbureted, electronic fuelinjected and direct fuel injected two-cycle engines, including: outboardmotors, snowmobiles, motorcycles, mopeds, ATVs, golf carts, lawn mowers,chain saws, string trimmers and the like.

Base Oil:

The lubricant base oils used in the two-cycle gasoline engine lubricantcompositions are, derived from substantially paraffinic waxy feeds. Theterm “substantially paraffinic” means containing a high level ofn-paraffins, generally greater than 40 wt %. Some substantiallyparaffinic waxy feeds may have for example greater than 50 wt %, orgreater than 75 wt % n-paraffins. One example of a substantiallyparaffinic waxy feed is wax produced in a Fischer-Tropsch process.Another example is highly refined slack wax.

Fischer-Tropsch waxes can be obtained by well-known processes such as,for example, the commercial SASOL® Slurry Phase Fischer-Tropschtechnology, the commercial SHELL® Middle Distillate Synthesis (SMDS)Process, or by the non-commercial EXXON® Advanced Gas Conversion(AGC-21) process. Details of these processes and others are describedin, for example, EP-A-776959, EP-A-668342; U.S. Pat. Nos. 4,943,672,5,059,299, 5,733,839, and RE39073, and US Published Application No,2005/0227866, WO-A-9934917, WO-A-9920720 and WO-A-05107935. TheFischer-Tropsch synthesis product usually comprises hydrocarbons having1 to 100, or even more than 100 carbon atoms, and typically includesparaffins, olefins and oxygenated products. Fischer Tropsch is a viableprocess to generate clean alternative hydrocarbon products, includingFischer-Tropsch waxes.

Slack wax can be obtained from conventional petroleum derived feedstocksby either hydrocracking or by solvent refining of the lube oil fraction.Typically, slack wax is recovered from solvent dewaxing feedstocksprepared by one of these processes. Hydrocracking is usually preferredbecause hydrocracking will also reduce the nitrogen content to a lowvalue. With slack wax derived from solvent refined oils, deoiling may beused to reduce the nitrogen content and raise the viscosity index.Hydrotreating of the slack wax can be used to lower the nitrogen andsulfur content. Slack waxes posses a very high viscosity index, normallyin the range of from about 140 to 200, depending on the oil content andthe starting material from which the slack wax was prepared. Therefore,slack waxes are suitable for the preparation of base oils used intwo-cycle gasoline engine lubricants.

In one embodiment the waxy feed has less than 25 ppm total combinednitrogen and sulfur. Nitrogen is measured by melting the waxy feed priorto oxidative combustion and chemiluminescence detection by ASTM D4629-02. The test method is further described in U.S. Pat. No.6,503,956, incorporated herein. Sulfur is measured by melting the waxyfeed prior to ultraviolet fluorescence by ASTM D 5453-00. The testmethod is further described in U.S. Pat. No. 6,503,956, incorporatedherein.

Determination of normal paraffins (n-paraffins) in wax-containingsamples should use a method that can determine the content of individualC7 to C110 n-paraffins with a limit of detection of 0.1 wt %. The methodused is described later in this disclosure.

Waxy feeds are expected to be plentiful and relatively cost competitivein the near future as large-scale Fischer-Tropsch synthesis, processescome into production. Fischer-Tropsch derived base oils made from thesewaxy feeds, and thus the two-cycle gasoline engine lubricants comprisingthem will be less expensive than lubricants made with other syntheticoils such as polyalphaolefins or esters. The terms “Fischer-Tropschderived” or “FT derived” means that the product fraction, or feedoriginates from or is produced at some stage by a Fischer-Tropschprocess. The feedstock for a Fischer-Tropsch process may come from awide variety of hydrocarbonaceous resources, including biomass, naturalgas, coal, shale oil, petroleum, municipal waste, derivatives of these,and combinations thereof. Syncrude prepared from the Fischer-Tropschprocess comprises a mixture of various solid, liquid, and gaseoushydrocarbons. Those Fischer-Tropsch products which boil within the rangeof lubricating base oil contain a high proportion of wax which makesthem ideal candidates for processing into base oil. Accordingly,Fischer-Tropsch wax represents an excellent fed for preparing highquality base oils. Fischer-Tropsch wax is normally solid at roomtemperature and, consequently, displays poor low temperature properties,such as pour point and cloud point. However, followinghydroisomerization of the wax, Fischer-Tropsch derived base oils havingexcellent low temperature properties may be prepared. A generaldescription of examples of suitable hydroisomerization dewaxingprocesses nay be found in U.S. Pat. Nos. 5,135,638 and 51282,958, and USPatent Application 20050133409, incorporated herein.

The hydroisomerization is achieved by contacting the wax feed with ahydroisomerzation catalyst in an isomerization zone underhydroisomerizing conditions. The hydroisomerization catalyst preferablycomprises a shape selective intermediate pore size molecular sieve, anoble metal hydrogenation component, and a refractory oxide support. Theshape selective intermediate pore size molecular sieve is preferablyselected from the group consisting of SAPO-11, SAPO-31, SAPO-41, SM-3,ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ 32, offretite, ferrierite,and combinations thereof. SAPO-11, ZSM-3, SSZ-32, ZSM-23, ZSM-48, andcombinations thereof are used in one embodiment. In one embodiment thenoble metal hydrogenation component is platinum, palladium, orcombinations thereof.

The hydroisomerizing conditions depend on the waxy feed used thehydroisomerization catalyst used, whether or not the catalyst issulfided, the desired yield, and the desired properties of the base oil.Examples of hydroisomerizing conditions of one embodiment includetemperatures of 260 degrees C. to about 413 degrees C. (500 to about 775degrees F.); a total pressure of 15 to 3000 psig, or 50 to 1000 psig;and a hydrogen to feed ratio from about 2 to 30 MSCF/bbl, about 4 to 20MSCF/bbl (about, 712.4 to about 3562 liter H₂/liter oil), about 4.5 or 5to about 10 MSCF/bbl, or about 5 to about 8 MSCF/bbl. Generally,hydrogen will be separated from the product and recycled to theisomerization zone. Note that a feed rate of 10 MSCF/bbl is equivalentto 1781 liter 1H2/liter feed. Generally, hydrogen will be separated fromthe product and recycled to the isomerization zone.

Optionally, the base oil produced by hydroisomerizaton dewaxing may behydrofinished. The hydrofinishing may occur in one or more steps, eitherbefore or after fractionating of the base oil into one or morefractions. The hydrofinishing is intended to improve the oxidationstability, UV stability, and appearance of the product by removingaromatics, olefins, color bodies, and solvents. A general description ofhydrofinishing may be found in U.S. Pat. Nos. 3,852,207 and 4,673,487,incorporated herein. The hydrofinishing step may be needed to reduce theweight percent olefins in the base oil to less than 10, less than 5 or2, less than 1, less than 0.5, and less than 0.05 or 0.01. Thehydrofinishing step may also be needed to reduce the weight percentaromatics to less than 0.3 or 0.1, less than 0.05, less than 0.02, andin some embodiments even less than 0.01.

Optionally, the base oil produced by hydroisomerization dewaxing may betreated with an adsorbent such as bauxite or clay to remove impuritiesand improve the color and biodegradability.

Because it is made from a waxy feed, the base oil has consecutivenumbers of carbon atoms. By “consecutive numbers of carbon atoms” wemean that the hydrocarbon molecules of the base oil differ from eachother by consecutive numbers of carbon atoms, as a consequence of thewaxy feed also having sequential numbers of carbon atoms. For example,in the Fischer-Tropsch hydrocarbon synthesis reaction the source ofcarbon atoms is CO and the hydrocarbon molecules are built up one carbonatom at a time. Petroleum-derived waxy feeds also have sequentialnumbers of carbon numbers. In contrast to an oil based on PAO, themolecules of the base oil have a more linear structure, comprising arelatively long backbone with short branches. The classic textbookdescription of a PAO is a star-shaped molecule, and in particulartridecane, which is illustrated as three decane molecules attached at acentral point. While a star-shaped molecule is theoretical, neverthelessPAO molecules have fewer and longer branches that the hydrocarbonmolecules that make up the base oil used in this disclosure. In anotherembodiment the base oil having consecutive numbers of carbon atoms alsohas less than 10 wt % naphthenic carbon by n-d-M.

In one embodiment the lubricating base oil is separated into fractions,whereby one or more of the fractions will have a pour point less than 0°C., less than −9° C., less than −15° C. less than −20° C., less than−30° C., or less than −35° C. Pour point is measured by ASTM D 5950-02.The base oil is optionally fractionated into different viscosity gradesof base oil. In the context of this disclosure “different viscositygrades of base oil” is defined as two or more base oils differing inkinematic viscosity at 100 degrees C. from each other by at least 0.5mm²/s, Kinematic viscosity is measured using ASTM D4475-06.Fractionating is done using a vacuum distillation unit to yield cutswith pre selected boiling ranges. One of the fractions may be adistillation bottoms product.

In one embodiment the base oil fractions have less than 0.01 wt %aromatic carbon and greater than about 90 wt % paraffinic carbon. Thebalance of the wt % carbon is naphthenic carbon. Wt % aromatic, wt %paraffinic and wt % naphthenic carbon are determined by n-d-M analysisaccording to ASTM D3238-95 (2005). In one embodiment the wt % paraffiniccarbon is between about 90 wt % and about 97 wt % and the wt %naphthenic carbon is between about 3 wt % and about 10 wt %.

In one embodiment, the viscosity indexes of the lubricating base oilfractions will be high. They will often have viscosity indexes greaterthan 28×Ln(Kinematic Viscosity at 100° C.)+80. In one embodiment theywill have viscosity indexes greater than 28×Ln(Kinematic Viscosity at100° C.)+95. For example a 2.5 mm²/s oil will have a viscosity indexgreater than 106, optionally greater than 121; and a 12 mm²/s oil willhave a viscosity index greater than 150 optionally greater than 165.

In another embodiment the base oil has a pour point of less than −8° C.a kinematic viscosity at 100° C. of at least 1.5 mm²/s; and a viscosityindex greater than an amount calculated by the equation: 22×Ln(Kinematic Viscosity at 100° C.)+132. In this embodiments for example,an oil with a kinematic viscosity of 2.5 mm²/s at 100° C. will have aviscosity index greater than 152. Base oils with these properties aredescribed in US Patent Publication US520050077208. The term “Ln” in thecontext of equations in this disclosure refers to the natural logarithmwith base ‘e’. The test method used to measure viscosity index is ASTMCD 227004.

The base oil fractions have a kinematic viscosity at 100° C. betweenabout 1.3 and 25 mm²/s. In one embodiment the base oil fractions have akinematic viscosity at 100° C. between about 1.5 and about 3.5 mm²/s. Inanother embodiment the base oil fractions have a kinematic viscositybetween about 1.8 and about 3.2 mm²/s.

In one embodiment, the base oil fraction provides excellent oxidationstability, low Noack volatility, as well as desired additive solubilityand elastomer compatibility. The base oil fractions have a weightpercent olefins less than 10, less than 5, less than 1, less than 0.5,or less than 0.05 or 0.01. The base oil fractions have a weight percentaromatics less than 0.1, less than 0.05, or less than 0.02.

“Traction coefficient” is an indicator of intrinsic lubricantproperties, expressed as the dimensionless ratio of the friction force Fand the normal force N, where friction is the mechanical force whichresists movement or hinders movement between sliding or rollingsurfaces. Traction coefficient can be measured with an MTM TractionMeasurement System from PCS Instruments, Ltd., configured with apolished 19 mm diameter ball (SAE AISI 52100 steel) angled at 220 to aflat 46 mm diameter polished disk (SAE AISI 52100 steel). The steel balland disk are independently measured at an average rolling speed of 3meters per second, a slide to roll ratio of 40 percent, and a load of 20Newtons. The roll ratio is defined as the difference in sliding speedbetween the ball and disk divided by the mean speed of the ball anddisk, i.e. roll ratio (Speed1−Speed2)/((Speed1+Speed2)−/2). In someembodiments, the base oil fractions have a traction coefficient lessthan 0.023, less than or equal to 0.021, or less than or equal to 0.019,when measured at a kinematic viscosity of 15 mm²/s and at a slide toroll ratio of 40 percent. In one embodiment they have a tractioncoefficient less than an amount defined by the equation: tractioncoefficient=0.009×Ln(Kinematic Viscosity)−0.001, wherein the KinematicViscosity during the traction coefficient measurement is between 2 and50 mm²/s; and wherein the traction coefficient is measured at an averagerolling speed of 3 meters per second, a slide to roll ratio of 40percent, and a load of 20 Newtons.

In one embodiment the base oil fractions have a traction coefficientless than 0.015 or less than 0.011, when measured at a kinematicviscosity of 15 mm²/s and at a slide to roll ratio of 40 percent.Examples of these base oil fractions with low traction coefficients aretaught in U.S. Pat. No. 7,045,055 and U.S. patent application Ser. Nos.11/400,570 and 11/399,773 both filed Apr. 7, 2006. In one embodiment,the base oil has a traction coefficient less than 0.015, and a 50 wt %boiling point greater than 565° C. (1050° F.). In another embodiment,the base oil has a traction coefficient less than 0.011 and a 50 wt %boiling point by ASTM D 6352-04 greater than 582° C. (1080° F.).

In some embodiments, the isomerized base oil having a low tractioncoefficient also displays unique branching properties by NMR, includinga branching index less than or equal to 23.4, a branching proximitygreater than or equal to 22.0, and a Free Carbon Index between 9 and 30.In one embodiment, the base oil has at least 4 wt % naphthenic carbon,in another embodiment, at least 5 wt % naphthenic carbon by n-d-Manalysis by ASTM D 3238-95 (Reapproved 2005). Two-cycle gasoline enginelubricants made comprising base oil fractions having low tractioncoefficients provide reduced engine wear.

In some embodiments, where the olefin and aromatics contents aresignificantly low in the lubricant base oil fraction of the lubricatingoil, the Oxidator BN of the selected base oil fraction will be greaterthan 25 hours, such as greater than 35 hours or even greater than 40hours. The Oxidator BN of the selected base oil fraction will typicallybe less than 70 hours. Oxidator BN is a convenient way to measure theoxidation stability of base oils. The Oxidator BN test is described byStangeland et al. in U.S. Pat. No. 3,852,207. The Oxidator BN testmeasures the resistance to oxidation by means of a Dornte-type oxygenabsorption apparatus. See R. W. Dornte “Oxidation of White Oils,”Industrial and Engineering Chemistry Vol 28, page 26, 1936. Normally,the conditions are one atmosphere of pure oxygen at 340° F. The resultsare reported in hours to absorb 1000 ml of O2 by 100 g, of oil. In theOxidator BN test, 0.8 ml of catalyst is used per 100 grams of oil and anadditive package is included in the oil. The catalyst is a mixture ofsoluble metal naphthenates in kerosene. The mixture of soluble metalnaphthenates simulates the average metal analysis of used crankcase oil.The level of metals in the catalyst is as follows: Copper=6,927 ppm;Iron=4,083 ppm; Lead=80,208 ppm; Manganese 350 ppm; Tin 3565 ppm. Theadditive package is 80 millimoles of zincbispolypropylenephenyldithio-phosphate per 100 grams of oil, orapproximately 1.1 grams of OLOA™ 260. The Oxidator BN test measures theresponse of a lubricating base oil in a simulated application. Highvalues, or long times to absorb one liter of oxygen, indicate goodoxidation stability. Two-cycle gasoline engine lubricants comprisingbase oil fractions having good oxidation stability will also haveimproved oxidation stability.

OLOA™ is an acronym for Oronite Lubricating Oil Additive, which is aregistered trademark of Chevron Oronite.

In some embodiments the one or more lubricating base oil fractions willhave excellent biodegradability. With suitable hydro-processing and/oradsorbent treatment they are readily biodegradable by the OECD 301BShake Flask Test (Modified Sturm Test). When the readily biodegradablebase oil fractions are blended with suitable biodegradable additives,such as selected low-ash or ashless additives, the lubricants willprovide rapid biodegradation of spills in sensitive areas with minimalnon-biodegradable residue and will prevent costly environmentalclean-up.

In some embodiments the one or more lubricating base oil fractions willhave a low Noack volatility. Noack volatility is usually testedaccording to ASTM D5800-05 Procedure B. In an embodiment, the one ormore lubricating base oil fractions have a Noack volatility of less than100 weight %. Noack volatility of base oils generally increases as thekinematic viscosity decreases. The lower the Noack volatility, the lowerthe tendency of base oil and formulated oils to volatilize in service.

The “Noack Volatility Factor” of base oil is an empirical number derivedfrom the kinematic viscosity of the base oil. The Noack volatility ofthe base oil derived from highly paraffinic wax is very low, and in anembodiment, is less than an amount calculated by the equation:

Noack Volatility Factor (1)=160−40(Kinematic Viscosity at 100° C.).

Equation (1), as provided in U.S. Patent Application Publication No.2006/0201852 A1, provides Noack Volatility Factors between 0 and 100 forkinematic viscosities between 1.5 and 4.0 mm²/s. FIG. 1 is a graph ofthe Noack Volatility Factor according to Equation (1). In a secondembodiment, the Noack volatility of the one or more lubricant base oilfractions is less than an amount calculated by the equation:

Noack Volatility Factor (2)=(900×(Kinematic Viscosity at 100°C.)^(−2.8))−15.

Equation (2), as provided in U.S. patent application Ser. No.11/613,936, provides Noack Volatility Factors between 0 and 100 forkinematic viscosities between 2.09 and 4.3 mm²/s. FIG. 1 also includesthe Noack Volatility Factor according to Equation (2). For kinematicviscosities in the range of 2.4 to 3.8 mm²/s, Equation (2) provides alower Noack Volatility Factor than does Equation (1). Lower NoackVolatility Factors in the range of base oils having kinematicviscosities from 2.4 to 3.8 mm²/s are desired, especially if the baseoils are to be blended with other oils that may have higher Noackvolatilities.

Additional base oils may be incorporated in the lubricant composition inan amount from about 1.0 wt % to about 20 wt % Examples of theseadditional base oils include esters, mixtures of esters, and complexesters as described in U.S. Pat. No. 6,197,731; polyalphaolefins,polyinternalolefins, polyisobutenes, alkylated aromatics such asalkylated naphthalenes, and conventional petroleum derived API Group IIand Group III mineral oils.

Pour Point Reducing Blend Component:

The two-cycle gasoline engine lubricant may comprise a pour pointreducing blend component. As used herein, “pour point reducing blendcomponent” refers to an isomerized wax product with relatively highmolecular weight and a specified degree of alkyl branching in themolecules, such that it reduces the pour point of lubricating base oilblends containing it. Examples of a pour point reducing blend componentare disclosed in U.S. Pat. Nos. 6,150,577 and 7,053,254, and PatentPublication No. US 20050247600 A1. A pour point reducing blend componentcan be: 1) an isomerized Fischer-Tropsch derived bottoms product; 2) abottoms product prepared from an isomerized highly waxy mineral oil, or3) an isomerized oil having a kinematic viscosity at 100° C. of at leastabout 8 mm²/s made from polyethylene plastic.

In one embodiment, the pour point reducing blend component is anisomerized Fischer-Tropsch derived vacuum distillation bottoms producthaving an average molecular weight between 600 and 1100 and an averagedegree of branching in the molecules between 6.5 and 10 alkyl branchesper 100 carbon atoms. Generally, the higher molecular weighthydrocarbons are more effective as pour point reducing blend componentsthan the lower molecular weight hydrocarbons. In one embodiment, ahigher cut point in a vacuum distillation unit which results in a higherboiling bottoms material is used to prepare the pour point reducingblend component. The higher cut point also has the advantage ofresulting in a higher yield of the distillate base oil fractions. In oneembodiment, the pour point reducing blend component is an isomerizedFischer-Tropsch derived vacuum distillation bottoms product having apour point that is at least 3° C. higher than the pour point of thedistillate base oil it is blended with.

In one embodiment, the 10 percent point of the boiling range of the pourpoint reducing blend component that is a vacuum distillation bottomsproduct is between about 850° F.-1050° F. (454-565° C.). In anotherembodiment, the pour point reducing blend component is derived fromeither Fischer-Tropsch or petroleum products, having a boiling rangeabove 950° F. (51000), and contains at least 50 percent by weight ofparaffins. In yet another embodiment the pour point reducing blendcomponent has a boiling range above 1050° F. (565° C.).

In another embodiment, the pour point reducing blend component is anisomerized petroleum derived base oil containing material having aboiling range above about 1050° F. In one embodiment, the isomerizedbottoms material is solvent dewaxed prior to being used as a pour pointreducing blend component. The waxy products further separated duringsolvent dewaxing from the pour point reducing blend component were foundto display excellent improved pour point depressing properties comparedto the oily product recovered after the solvent dewaxing.

In another embodiment, the pour point reducing blend component is anisomerized oil having a kinematic viscosity at 1000 of at least about 8mm2/s made from polyethylene plastic. In one embodiment the pour pointreducing blend component is made from waste plastic. In anotherembodiment the pour point reducing blend component is made from stepscomprising pyrolysis of polyethylene plastic, separating, out a heavyfraction, hydrotreating the heavy fraction, catalytic isomerizing thehydrotreated heavy fraction, and collecting the pour point reducingblend component having a kinematic viscosity at 100° C. of at leastabout 8 mm2/s. In a third embodiment, the pour point reducing blendcomponent derived from polyethylene plastic and has a boiling rangeabove 1050° F. (565° C.), or even has a boiling range above 1200° F.(649° C.).

In one embodiment, the pour point reducing blend component has anaverage degree of branching in the molecules within the range of from6.5 to 10 alkyl branches per 100 carbon atoms. In another embodiment thepour point reducing blend component has an average molecular weightbetween 600-1100. In a third embodiment it has an average molecularweight between 700-1000. In one embodiment, the pour point reducingblend component has a kinematic viscosity at 100° C. of 8-30 mm²/s, withthe 10% point of the boiling range failing be en about 850-1050° F. Inyet another embodiment, the pour point reducing blend component has akinematic viscosity at 100° C. of 15-20 mm²/s and a pour point of −8 to−12° C.

In one embodiment, the pour point reducing blend component is anisomerized oil having a kinematic viscosity at 100° C. of at least about8 mm²/s made from polyethylene plastic. In one embodiment the pour pointreducing blend component is made from waste plastic. In anotherembodiment the pour point reducing blend component is made from stepscomprising pyrolysis of polyethylene plastic, separating out a heavyfraction, hydrotreating the heavy fraction, catalytic isomerizing thehydrotreated heavy fraction, and collecting the pour point reducingblend component having a kinematic viscosity at 1000 of at least about 8mm²/s. In a third embodiment, the pour point reducing blend componentderived from polyethylene plastic has a boiling range above 1050° F.(565° C.), or even a boiling range above 1200° F. (649° C.).

Additives & Additive Packages:

Various detergent/dispersant additive packages may be combined with baseoil in formulating two-cycle oil gasoline engine lubricants. Ashless,low-ash, or ash-containing additives may be used for this purpose.

Suitable ashless additives include polyamide, alkenylsuccinimides, boricacid-modified alkenylsuccinimides, phenolic amines and succinatederivatives or combinations of any two or more of such additives.

Examples of a low ash additive package comprise (i) polyisobutenyl (Mn400-2500) succinimide or another oil soluble, acylated, nitrogencontaining lubricating oil dispersant present in the amount of 0.2-5 wt.% in the lubricating oil and (ii) a metal phenate, sulfonate orsalicylate oil soluble detergent additive. In one embodiment, the oilsoluble detergent additive is a neutral metal detergent or overbasedmetal detergent of Total Base Number 200 or less, present in the amountof 0.1-2 wt % in the lubricating oil. In this embodiment the metal iscalcium, barium or magnesium. Neutral calcium salicylates are oneexample) and may be present in amounts of about 0.5 to 1.5 wt % in thelubricating oil.

Polyamide detergent/dispersant additives, such as the commonly usedtetraethylenepentamine isostearate, may be prepared by the reaction offatty acid and polyalkylene polyamines, as described in U.S. Pat. No.3,169,980, the entire disclosure of which is incorporated by referencein this specification, as if set forth herein in full. These polyamidesmay contain measurable amounts of cyclic imidazolines formed by internalcondensation of the linear polyamides upon continued heating at elevatedtemperature. Another useful class of polyamide additives is preparedfrom polyalkylene polyamines and C19-C25 Koch acids, according to theprocedure of R. Hartle: et al., JAOCS, 57 (5), 156-59 (1980).Alkenylsuccinimides are formed by a step-wise procedure in which anolefin such as polybutene (MV 1200) is reacted with maleic anhydride toyield a polybutenyl succinic anhydride adduct, which is then reactedwith an amine, e.g., an alkylamine or a poly-amine, to form the desiredproduct.

Phenolic amines are prepared by the well-known Mannich reaction (C.Mannich and W. Krosche. Arch. Pharm., 250: 674 (1912)), involving apolyalkylene-substituted phenol, formaldehyde and a polyalkylenepolyamine.

Succinate derivatives are prepared by the reaction of an olefin (e.g.,polybutene (eg., polybutene) and maleic anhydride to yield a polybutenylsuccinic anhydride adduct, which undergoes further reaction with apolyol, e.g., pentaerythritol, to give the desired product.

Suitable ash-Containing detergent/dispersant additives include alkalineearth metal (e.g., magnesium, calcium, barium), sulfonates, phosphonatesor phenates or combinations of any two or more of such additives.

The foregoing detergent/dispersant additives may be incorporated in thelubricant compositions described herein in an amount from about 1 toabout 25 wt %, and more preferably from about 3 to about 20 wt % basedon the total weight of the composition.

Commercially available two-cycle lubricant detergent/dispersant additivepackages may be used in combination with the base oil to produce thetwo-cycle gasoline engine lubricant, for example, LUBRIZOL 400, LUBRIZOL6827, LUBRIZOL 6830, LUBRIZOL 600, LUBRIZOL 606, ORONITE OLOA® 9333,ORONITE OLOA® 340A, ORONITE OLOA® 6721 and ORONITE OLOA® 9357.

Various other additives may be incorporated in the two-cycle gasolineengine lubricant, as desired. These include smoke-suppression agents,such as polybutene or polyisobutylene (PIB), extreme pressure additives,such as dialkyldithiophosphoric acid salts or esters, anti-foamingagents, such as silicone oil, pour point depressants, rust or corrosionprevention agents, such as triazole derivatives, propyl gallate oralkali metal phenolates or sulfonates, oxidation inhibitors, such assubstituted diarylamines, phenothiazines, hindered phenols, or the like.Certain of these additives may be multifunctional, such aspolymethacrylate, which may serve as an anti-foaming agent, as well as apour point depressant. Pour point depressants, when used, are used in anamount between 0.005 to 0.1 wt % based on the total lubricating oil.Examples of pour point depressants are polymethacrylates (PMA);polyacrylates; polyacrylamides; condensation products of haloparaffinwaxes and aromatic compounds; vinyl carboxylate polymers; terpolymers ofdialkylfumarates, vinyl esters of fatty acids, and alkyl vinyl ethers;and mixtures thereof.

In one embodiment, the smoke-suppression agent is an olefinicallyunsaturated polymer selected from the group consisting of polybutene,polyisobutylene or a mixture of polybutene and polyisobutylene, whichhas a number average molecular weight of 400 to 2200 and a terminalvinylidene content of at least 60 mol %, based on the total number ofdouble bonds in the polymer. These types of smoke-suppression agents aretaught in EP1743932A. A commercial example of these smoke-suppressionagents is BASF Corporation's GLISSOPAL® 1000.

Volatile, combustibles high flash hydrocarbon solvent such as kerosene,Exxsol D80, or Stoddard solvent can also be used as additives. ExxsolD80 is a dearomatized aliphatic high flash solvent with an initialboiling point of at least 200° C., a Kauri-Butanol Value of about 28(between 20 and 40), and an aniline point of 73.9 to 79.4° C. Volatile,combustible high flash hydrocarbon solvents may be added to thetwo-cycle engine lubricant in an amount less than 5 wt % of the totallubricating oil in order to bring the s-moke index to a value of atleast 75 in the JASO M 342-92 test and/or to improve the compatibilityand/or solubility of other additives and to improve the low temperaturecharacteristics such as viscosity and gasoline miscibility. In oneembodiment, the trio-cycle gasoline engine lubricant comprises lowlevels of solvent, such as less than about 5 wt %, less than about 2 wt%, or even essentially none of the total lubricating oil is ahydrocarbon solvent having a maximum boiling point less than 250 degrees0° C. Lower levels of solvent in the two-cycle gasoline engine lubricantprovides for reduced pollution by evaporation of volatile organiccontents, improved compatibility with elastomers used in packaging andtransport, and reduced flammability hazards for enhanced transportationand storage safety.

Most of the above-described additives may be incorporated in thelubricant composition in an amount from about 0.005% to about 15%, orfrom about 0.005% to about 6%, based on the total weight of thelubricant composition. In the case of polybutene or polyisobutylene, theamount may vary from 1% to 50%. The amount of each additive or additivepackage selected within the specified range should be such as not toadversely effect the desirable performance properties of the lubricant.The effects produced by such additives can be readily determined byroutine testing.

Alternatively, the lubricating oil is one consisting of, or consistingessentially of:

-   -   a. between 20 and 70 wt % based on the total lubricating oil of        one or more base oil fractions having:        -   i. consecutive numbers of carbon atoms;        -   ii. a kinematic viscosity at 100° C. between about 1.5 and            about 3.5 mm²/s.        -   iii. between about 90 wt % and about 97 wt % paraffinic            carbon;        -   iv. between about 3 wt % and about 10 wt % naphthenic            carbon;        -   v. less than 0.01 wt % aromatic carbon;    -   b. between 0.5 and 25 wt % based on the total lubricating oil of        a pour point reducing blend component;    -   c. less than about 5 wt % based on the total lubricating oil of        a hydrocarbon solvent having a maximum boiling point less than        250 degrees C.    -   d. from about 1 wt % to about 25 wt % based on the total        lubricating oil of a detergent/dispersant additive package;    -   e. from about 1 wt % to about 50 wt % based on the total        lubricating oil of a smoke-suppression agent; and    -   f. less than 0.1 wt % based on the total lubricating oil of a        pour point depressant;        wherein the lubricating oil has a blend kinematic viscosity at        100° C. of 6.5 mm²/s or greater, good low temperature fluidity        at −25° C., and an exhaust smoke index of greater than 65.

The two-cycle gasoline engine lubricants have high flash points due tothe low level of solvent they contain. Their flash points are in someembodiments greater than 120° C., or greater than 150° C.

Specific Analytical Test Methods: Wt % Normal Paraffins inWax-Containing Samples:

Quantitative analysis of normal paraffins in wax-containing samples isdetermined by gas chromatography (GC). The GO (Agilent 6890 or 5890 withcapillary split/splitless inlet and flame ionization detector) isequipped with a flame ionization detector, which is highly sensitive tohydrocarbons. The method utilizes a methyl silicone capillary column,routinely used to separate hydrocarbon mixtures by boiling point. Thecolumn is fused silica, 100% methyl silicone, 30 meters length, 0.25 mmID, 0.1 micron film thickness supplied by Agilent. Helium is the carriergas (2 ml/min) and hydrogen and air are used as the fuel to the flame.

The waxy feed is melted to obtain a 0.1 g homogeneous sample. The sampleis immediately dissolved in carbon disulfide to give a 2 wt % solution.If necessary, the solution is heated until visually clear and free ofsolids, and then injected into the GC. The methyl silicone column isheated using the following temperature program:

-   -   Initial temp: 150° C. (if C7 to C15 hydrocarbons are present,        the initial temperature is 50° C.)    -   Ramp: 600 per minute    -   Final Temp: 400° C.    -   Final hold: 5 minutes or until peaks no longer elute

The column then effectively separates, in the order of rising carbonnumber, the normal paraffins from the non-normal paraffins. A knownreference standard is analyzed in the same manner to establish elutiontimes of the specific normal-paraffin peaks. The standard is ASTM D2887n-paraffin standard, purchased from a vendor (Agilent or Supelco),spiked with 5 wt % Polywax 500 polyethylene (purchased from PetroliteCorporation in Oklahoma). The standard is melted prior to injection.Historical data collected from the analysis of the reference standardalso guarantees the resolving efficiency of the capillary column.

If present in the sample, normal paraffin peaks are well separated andeasily identifiable from other hydrocarbon types present in the sample.Those peaks eluting outside the retention time of the normal paraffinsare called non-normal paraffins. The total sample is integrated usingbaseline hold from start to end of run. N-paraffins are skimmed from thetotal area and are integrated from valley to valley. All peaks detectedare normalized to 100%. EZChrom is used for the peak identification andcalculation of results.

Wt % Olefins:

The Wt % Olefins in the base oils is determined by proton-NMR by thefollowing steps, A-D;

-   -   A. Prepare a solution of 5-10% of the test hydrocarbon in        deuterochloroform.    -   B. Acquire a normal proton spectrum of at least 12 ppm spectral        width and accurately reference the chemical shift (ppm) axis.        The instrument must have sufficient gain range to acquire a        signal without overloading the receiver/ADG. When a 30 degree        pulse is applied, the instrument must have a minimum signal        digitization dynamic range of 65,000. Preferably the dynamic        range will be 260,000 or more.    -   C. Measure the integral intensities between:    -   6.0-4.5 ppm (olefin)    -   2.2-1.9 ppm (allylic)    -   1.9-0.5 ppm (saturate)    -   D. Using the molecular weight of the test substance determined        by ASTM D2503% calculate:        -   1. The average molecular formula of the saturated            hydrocarbons        -   2. The average molecular formula of the olefins        -   3. The total integral intensity (=sum of all integral            intensities)        -   4. The integral intensity per sample hydrogen (=total            integral/number of hydrogens in formula)        -   5. The number of olefin hydrogens (=Olefin integral/integral            per hydrogen)        -   6. The number of double bonds (=Olefin hydrogen times            hydrogens in olefin formula/2)        -   7. The wt % olefins by proton NMR=100 times the number of            double bonds times the number of hydrogens in a typical            olefin molecule divided by the number of hydrogens in a            typical test substance molecule.

The wt % olefins by proton NMR calculation procedure, D, works best whenthe % olefins result is low, less than about 15 weight percent. Theolefins must be “conventional” olefins, i.e. a distributed mixture ofthose olefin types having hydrogens attached to the double bond carbonssuch as: alpha, vinylidene, cis, trans, and trisubstituted. These olefintypes will have a detectable allylic to olefin integral ratio between 1and about 2.5. When this ratio exceeds about 3, it indicates a higherpercentage of tri or tetra substituted olefins are present and thatdifferent assumptions must be made to calculate the number of doublebonds in the sample.

Aromatics Measurement by HPLC-UV:

The method used to measure low levels of molecules with at least onearomatic function in the lubricants base oils uses a Hewlett Packard1050 Series Quaternary Gradient High Performance Liquid Chromatography(HPLC) system coupled with a, HP 1050 Diode-Array UV-V is detectorinterfaced to an HP Chem-station. Identification of the individualaromatic classes in the highly saturated Base oils was made on the basisof their UV spectral pattern and their elution time. The amino columnused for this analysis differentiates aromatic molecules largely on thebasis of their ring-number (or more correctly, double-bond number).Thus, the single ring aromatic containing molecules elute first,followed by the polycyclic aromatics in order of increasing double bondnumber per molecule. For aromatics with similar double bond character,those with only alkyl substitution on the ring elute sooner than thosewith naphthenic substitution.

Unequivocal identification of the various base oil aromatic hydrocarbonsfrom their UV absorbance spectra was accomplished recognizing that theirpeak electronic transitions were all red-shifted relative to the puremodel compound analogs to a degree dependent on the amount of alkyl andnaphthenic substitution on the ring system. These bathochromic shiftsare well known to be caused by alkyl-group delocalization of theπ-electrons in the aromatic ring. Since few unsubstituted aromaticcompounds boil in the lubricant range, some degree of red-shift wasexpected and observed for all of the principle aromatic groupsidentified.

Quantitation of the eluting aromatic compounds was made by integratingchromatograms made from wavelengths optimized for each general class ofcompounds over the appropriated retention time window for that aromatic.Retention time window limits for each aromatic class were determined bymanually evaluating the individual absorbance spectra of elutingcompounds at different times and assigning them to the appropriatearomatic class based on their qualitative similarity to model compoundabsorption spectra. With few exceptions, only five classes of aromaticcompounds were observed in highly saturated API Group II and IIIlubricant base oils.

HPLC-UV Calibration:

HPLC-UV is used for identifying these classes of aromatic compounds evenat very low levels. Multi-ring aromatics typically absorb 10 to 200times more strongly than single-ring aromatics. Alkyl-substitution alsoaffected absorption by about 20%. Therefore, it is important to use HPLCto separate and identify the various species of aromatics and know howefficiently they absorb.

Five classes of aromatic compounds were identified. With the exceptionof a small overlap between the most highly retained alkyl-1-ringaromatic naphthenes and the least highly retained alkyl naphthalenes,all of the aromatic compound classes were baseline resolved. Integrationlimits for the co-eluting 1-ring and 2-ring aromatics at 272 nm weremade by the perpendicular drop method. Wavelength dependent responsefactors for each general aromatic class were first determined byconstructing Beer's Law plots from pure model compound mixtures based onthe nearest spectral peak absorbances to the substituted aromaticanalogs.

For example, alkyl-cyclohexylbenzene molecules in base oils exhibit adistinct peak absorbance at 272 nm that corresponds to the same(forbidden) transition that unsubstituted tetralin model compounds do at268 nm. The concentration of alkyl-1-ring aromatic naphthenes in baseoil samples was calculated by assuming that its molar absorptivityresponse factor at 272 nm was approximately equal to tetralin's molarabsorptivity at 268 nm, calculated from Beer's law plots. Weight percentconcentrations of aromatics were calculated by assuming that the averagemolecular weight for each aromatic class was approximately equal to theaverage molecular weight for the whole base oil sample.

This calibration method was further improved by isolating the 1-ringaromatics directly from the lubricant base oils via exhaustive HPLCchromatography. Calibrating directly with these aromatics eliminated theassumptions and uncertainties associated with the model: compounds. Asexpected, the isolated aromatic sample had a lower response factor thanthe model compound because it was more highly substituted.

More specifically, to accurately calibrate the HPLC-UV method, thesubstituted benzene aromatics were separated from the bulk of thelubricant base oil using a Waters semi-preparative HPLC unit. 10 gramsof sample was diluted 1:1 in n-hexane and injected onto an amino-bondedsilica column, a 5 cm×22.4 mm ID guard, followed by two 25 cm×22.4 mm IDcolumns of 8-12 micron amino-bonded silica particles, manufactured byRainin Instruments, Emeryville, Calif., with n-hexane as the mobilephase at a flow rate of 18 mls/min. Column eluent was fractionated basedon the detector response from a dual wavelength UV detector set at 265nm and 295 nm. Saturate fractions were collected until the 265 nmabsorbance showed a change of 0.01 absorbance units, which signaled theonset of single ring aromatic elution. A single ring aromatic fractionwas collected until the absorbance ratio between 265 nm and 295 nmdecreased to 2.0, indicating the onset of two ring aromatic elution.Purification and separation of the single ring aromatic fraction wasmade by re-chromatographing the monoaromatic fraction away from the“tailng” saturates fraction which resulted from overloading the HPLCcolumn.

This purified aromatic “standard” showed that alkyl substitutiondecreased the molar absorptivity response factor by about 20% relativeto unsubstituted tetralin.

Confirmation of Aromatics by NMR:

The weight percent of all molecules with at least one aromatic functionin the purified mono-aromatic standard was confirmed via long-durationcarbon 13 NMR analysis, NMR was easier to calibrate than HPLC UV becauseit simply measured aromatic carbon so the response did not depend on theclass of aromatics being analyzed. The NMR results were translated from% aromatic carbon to aromatic molecules (to be consistent with HPLC-UVand D 2007) by knowing that 95-99% of the aromatics in highly saturatedlubricant base oils were single-ring aromatics.

High power, long duration, and good baseline analysis were needed toaccurately measure aromatics down to 0.2% aromatic molecules.

More specifically, to accurately measure low levels of all moleculeswith at least one aromatic function by NMR, the standard D 5292-99method was modified to give a minimum carbon sensitivity of 500:1 (byASTM standard practice E 386). A 15-hour duration run on a 400-500 MHzNMR with a 10-12 mm Nalorac probe was used. Acorn PC integrationsoftware was used to define the shape of the baseline and consistentlyintegrate. The carrier frequency was changed once during the run toavoid artifacts from imaging the aliphatic peak into the aromaticregion. By taking spectra on either side of the carrier spectra, theresolution was improved significantly.

EXAMPLES Example 1

A wax sample composed of several different batches of hydrotreatedFischer-Tropsch wax, all made using a Co-based Fischer-Tropsch catalyst,was prepared. The different batches of wax composing the wax sample wereanalyzed and all found to have the properties as shown in Table II

TABLE II Fischer-Tropsch Wax Co-Based Fischer-Tropsch Catalyst Sulfur,ppm <10 Nitrogen, ppm <10 Oxygen, wt % <0.50 Wt % N-Paraffins by GC >85D 6352 SIMDIST TBP (WT %), ° F. T10 550-700 T90 1000-1080 T90-T10, ° C.>154

The Co-based Fischer-Tropsch wax was hydroisomerized over a Pt/SAPO-11catalyst with an alumina binder. Operating conditions includedtemperatures between 635° F. and 675° F. (335° C. and 358° C.), LHSV of1.0 hr⁻¹, reactor pressure of about 500 psig, and once-through hydrogenrates of between 5 and 6 MSCF/bbl. The reactor effluent passed directlyto a second reactor containing a Pd on silica-alumina hydrofinishingcatalyst also operated at 500 psig. Conditions in the second reactorincluded a temperature of about 350° F. (177° C.) and an LHSV of 2.0hr⁻¹.

The products boiling above 650° F. were fractionated by vacuumdistillation to produce distillate fractions of different viscositygrades. Three Fischer-Tropsch derived lubricant base oils were obtained.Two were distillate side-cut fractions (XLFTBO and XLFTBO) and one was adistillate bottoms fraction (HFTBO). Test data on the threeFischer-Tropsch derived lubricant base oils are shown in Table III,below.

TABLE III Sample Properties HFTBO XLFTBO XXLFTBO Viscosity at 100° C.,mm²/s 16.01 2.926 2.409 Viscosity Index 161 124 125 Pour Point, ° C. −10−37 −42 D 6352 SIMDIST TBP (WT %), ° F.  5 963 683 625 10/30 988/1040692/717 640/673 50 1074 737 696 70/90 1113/1181 755/777 716/738 95 1213785 746 Wt % Aromatics 0.0306 0.0131 0.0185 Wt % Olefins <0.1 <0.1 <0.1n-d-M Wt % Paraffinic Carbon 92.98 95.42 96.13 Wt % Naphthenic Carbon7.02 4.58 3.87 Wt % Aromatic Carbon 0.00 0.00 0.00 Oxidator BN, hours45.32 40.16 47.69 X in the equation: VI = 28 × Ln(VIS100) + X 83.4 93.9100 Noack volatility, wt % 0.95 32.37 54.1 NVF (1) = 160 − (40 × kV100)42.96 63.64 NVF (2) = (900 × (KV100) − ^(2.8)) − 15 29.5 61.75 AlkylBranches per 100 Carbons 7.58 Not tested 10.2 Traction Coefficient at 15mm²/s <0.015 Not tested 0.032 and at a slide to roll ratio of 40%

HFTBO is an example of a pour point reducing blend component with a lowtraction coefficient. XLFTBO is an example of a fraction of alubricating base oil having a Noack volatility less than a NoackVolatility Factor by Equation (1). XXLFTBO is an example of a fractionof a lubricating base oil having a Noack volatility less than a NoackVolatility Factor less than both a Noack Volatility Factor by Equation(1) and a Noack Volatility Factor by Equation (2).

Example 2

Chevron MOTEX 2T-X is a two-cycle outboard engine oil formulated withhigh quality mineral base oil, polyisobutylene, a high performance lowash detergent/dispersant additive package, and a high flash solvent.Three different blends of two-cycle gasoline engine lubricant using thesame high performance low ash detergent/dispersant additive package andpolyisobutylene synthetic base oil used in Chevron Motex 2T-X wereprepared (BlendB, BlendC, and BlendF) using the Fischer-Tropsch derivedbase oils described earlier. A comparison blend (COMP BlendA) usingconventional mineral base oil and high flash solvent was also prepared.The formulations of these blends are summarized in Table IV.

TABLE IV COMP Component, Wt % BlendA BlendB BlendC BlendF ExxonMobilAP/E 18.50 0 0 0 Core 600N ExxonMobil AP/E 29.00 0 0 0 Core 150N ExxsolD80 20.00 0 0 0 HFTBO 0 8.40 16.90 22.50 XLFTBO 0 0 0 XXL FTBO 0 59.1050.60 44.70 Two-cycle lubricant 5.50 5.50 5.50 5.50 detergent/dispersantadditive package PIB 27.00 27.00 27.00 27.00 Pour Point 0 0 0 0.3Depressant

The performance properties of three of these two-cycle gasoline enginelubricant blends are shown in Table V.

TABLE V COMP Properties BlendA BlendB BlendC BlendF Fluidity, mPa · s−10° C. 959 539 5230 Not tested −25° C. >7500 2579 Not tested 3489Miscibility −10° C. Pass Pass Not Tested Not Tested −25° C. Fail PassPass Pass Kin Vis @100° C., 8.058 7.137 9.13 8.082 mm²/s Viscosity Index136 160 156 153 Pour Point, ° C. −18 −40 −35 −49 Flash Point, ° C. 100Not Tested Not Tested 194 Aniline Point, ° C. 110 Not Tested Not Tested124 Sulfate Ash, wt % <0.15 <0.15 <0.15 <0.15 Detergency, 180- 152 148101 Not Tested minute evaluation Piston Skirt Deposit 112 110 95 NotTested Index Lubricity by JASCO 95 86 103 104 M340-92 Exhaust Smoke 9988 76 70 Index

Flash Points were measured by the Cleveland Open Cup Tester, using ASTMD92-05a. Aniline Points were measured by ASTMD D611-04. BlendB, BlendC,and BlendF had essentially no hydrocarbon solvent having a maximumboiling point less than 250 degrees C., yet they all had low exhaustsmoke index values, lower pour points, and improved miscibility comparedto COMP BlendA made with conventional mineral oil base oil and highflash solvent BlendF, comprising the highest level of HFTBO, gave anespecially high lubricity index, yet still had excellent miscibility anda good exhaust smoke index.

Example 3

A blend of two-cycle gasoline engine lubricant using adetergent/dispersant additive package designed to meet thespecifications for Thailand Domestic (TIS 1040-2541 [1998]) was preparedusing the Fischer-Tropsch derived base oils described earlier. Acomparison blend using conventional petroleum-derived base oil and highflash solvent was also prepared. The formulations of these blends aresummarized in Table VI

TABLE VI COMP Component, Wt % BlendD BlendE TPI 600N 30.95 0 Exxsol D8025.50 0 HFTBO 0 1.58 XLFTBO 0 0 XXLFTBO 0 54.87 Two-cycle lubricant 5.505.50 detergent/dispersant additive package PIB 38.00 38.00 PMA PourPoint Depressant 0.05 0.05

The performance properties of these two-cycle gasoline engine lubricantblends are shown in Table VII.

TABLE VII COMP Properties BlendD BlendE Fluidity, mPa · s −10° C. 14601160 −25° C. >7500 4799 Miscibility −10° C. Pass Pass −25° C. Fail PassKin Vis @100° C., 10.51 9.724 mm²/s Viscosity Index 133 148 Pour Point,° C. −32 −50 Flash Point, ° C. 92 182 Aniline Point, ° C. 116.4 122Sulfated Ash, wt % <0.18 <0.18 Detergency, 180- 131 151 minuteevaluation Piston Skirt Deposit 110 112 Index Exhaust Smoke Index 137 84

BlendE also comprised the pour point reducing blend component having alow traction coefficient, HFTBO. Note that this blend had had anespecially low pour point and good low temperature fluidity at −25° C.BlendE had better low temperature fluidity, lower pour point, bettergasoline miscibility, better detergency, and a better piston skirtdeposit index than COMP BlendD made with conventional mineral oil baseoil and greater than 5 wt % hydrocarbon solvent having a maximum boilingpoint less than 250 degrees C. BlendE, with the addition of less than 5wt % hydrocarbon solvent having a maximum boiling point less than 250degrees C., would easily pass the requirements of both JASO M345:2003and ISO 13738:2000(E), classifications C and D.

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Furthermore, all ranges disclosed herein are inclusive ofthe endpoints and are independently combinable.

All of the publications, patents and patent applications cited in thisapplication are herein incorporated by reference in their entirety tothe same extent as if the disclosure of each individual publication,patent application or patent was specifically and individually indicatedto be incorporated by reference in its entirety.

This written description uses examples to disclose the invention,including the best mode, and also to enable any person skilled in the atto make and use the inventions. Many modifications of the exemplaryembodiments of the invention disclosed above will readily occur to thoseskilled in the art. Accordingly, the invention is to be construed asincluding all structure and methods that fall within the scope of theappended claims.

1. A process to prepare a lubricating oil, comprising: a.hydroisomerization dewaxing a substantially paraffinic wax feed, wherebya lubricating base oil is produced; and b. blending one or morefractions of the lubricating base oil with: i. less than about 5 wt. %based on the total lubricating oil composition of a hydrocarbon solventhaving a maximum boiling point less than 250 degrees C., and ii. adetergent/dispersant additive package; whereby the lubricating oil meetsthe requirements of JASO M345:2003.
 2. The process of claim 1, whereinthe substantially paraffinic wax feed is Fischer-Tropsch derived.
 3. Theprocess of claim 2, wherein a feedstock for a Fischer-Tropsch processused to produce the substantially paraffinic wax feed is ahydrocarbonaceous resource selected from the group of biomass, naturalgas, coal, shale oil, petroleum, municipal waste, derivatives of these,and combinations thereof.
 4. The process of claim 1, wherein thehydroisomerization dewaxing uses a catalyst comprising a shape selectiveintermediate pore size molecular sieve, a noble metal hydrogenationcomponent, and a refractory oxide support.
 5. The process of claim 4,wherein the shape selective intermediate pore size molecular sieve isselected from the group consisting of SAPO-11, SAPO-31, SAPO-41, SM 3,ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, SSZ-32 offretite, ferrierite,and combinations thereof.
 6. The process of claim 4, wherein the noblemetal hydrogenation component is platinum, palladium, or combinationsthereof.
 7. The process of claim 1, comprising blending the one or morefractions of the lubricating base oil with less than about 2 wt % basedon the total lubricating oil composition of a hydrocarbon solvent havinga maximum boiling point less than 250 degrees C.
 8. The process of claim7 comprising blending the one or more fractions of the lubricating baseoil with essentially no hydrocarbon solvent.
 9. The process of claim 1,additionally comprising blending the one or more fractions of thelubricating base oil with a smoke-suppression agent selected from thegroup of polybutene, polyisobutylene, and mixtures thereof.
 10. Theprocess of claim 1 additionally comprising blending the one or morefractions of the lubricating base oil with a pour point depressant. 11.The process of claim 1, additionally comprising blending the one or morefractions of the lubricating base oil with a pour point reducing blendcomponent.
 12. The process of claim 1, wherein the one or more fractionsof the lubricating base oil have a kinematic viscosity at 100° C.between about 1.5 and about 3.5 mm²/s.
 13. The process of claim 1,wherein the one or more fractions of the lubricating base oil have aNoack volatility of less than 90 wt %.
 14. The process of claim 13,wherein the one or more fractions of the lubricating base oil have akinematic viscosity between 1.5 and 4.0 mm²/s and a Noack volatilityless than a Noack Volatility Factor (1)=160−(40×kinematic viscosity at100° C.).
 15. The process of claim 14, wherein the one or more fractionsof the lubricating base oil have a kinematic viscosity between 2.09 and4.0 mm²/s and a Noack volatility less than a Noack Volatility Factor(2)=(900×(kinematic viscosity at 100° C.)^(−2.8))−15.
 16. The process ofclaim 1, wherein the one or more fractions of the lubricating base oilhave greater than about 90 wt % paraffinic carbon and less than 0.01 wt% aromatic carbon by ASTM D3238-95 (2005).
 17. The process of claim 1wherein the one or more fractions of the lubricating base oil have anOxidator BN greater than 35 hours.
 18. The process of claim 1, whereinthe lubricating oil has a flash point by ASTM D92-05a greater than 120°C.
 19. The process of claim 1, wherein the lubricating base oil has aviscosity index greater than 28×Ln(KineMatic Viscosity at 100° C.)+95.20. A process for making a lubricating oil, comprising: a. blendingtogether: i. one or more fractions of base oil having a kinematicviscosity at 100° C. between about 1.5 and about 3.5 mm²/s, and ii. apour point reducing blend component, to produce a pour point reducedbase oil blend: b. adding to the pour point reduced base oil blend: i.a: detergent/dispersant additive package; ii. a smoke-suppression agent;iii optionally a pour point depressant; and iv. optionally less thanabout 5 wt % hydrocarbon solvent having a maximum boiling point lessthan 250 degrees C.; whereby a two-cycle gasoline engine lubricant isproduced.
 21. The process of claim 20, wherein the two-cycle gasolineengine lubricant has: (a) a good low temperature fluidity at −25° C.;(b) a passing result in the miscibility test by ASTM D4682-87(Reapproved 2002) at −25° C.; (c) an exhaust smoke index of greater than65; and (d) a pour point less than or equal to about −35° C.
 22. Theprocess of claim 20, wherein the one or more fractions of base oil aremade from a waxy feed.
 23. The process of claim 20, wherein the exhaustsmoke index is greater than or equal to
 85. 24. The process of claim 20,wherein the pour point is less than or equal to about −40° C.
 25. Theprocess of claim 20, wherein the smoke-suppression agent ispolyisobutylene.
 26. The process of claim 20, wherein the hydrocarbonsolvent is a dearomatized aliphatic solvent.
 27. The process of claim20, wherein essentially no hydrocarbon solvent is added.
 28. The processof claim 20, wherein the pour point reducing blend component has atraction coefficient less than 0.015 when measured at a kinematicviscosity of 15 mm²/s and at a slide to roll ratio of 40%.
 29. A processfor making a two-cycle gasoline engine lubricant meeting the JASOM345:2003 requirements, comprising: a. preparing a pour point reducingblend component by isomerizing a feed; b. blending the pour pointreducing blend component with i. a distillate base oil having akinematic viscosity at 100° C. between about 1.5 and about 3.5 mm²/s toproduce a pour point reduced base oil blend; c. blending the pour pointreduced base oil blend with: i. a detergent/dispersant additive package;and ii. less than 5 wt %/, based on the total two-cycle gasoline enginelubricant, of a hydrocarbon solvent having a maximum boiling point lessthan 250 degrees C.;  in the proper proportions to yield the two-cyclegasoline engine lubricant.
 30. The process of claim 29, wherein the feedis selected from the group of Fischer-Tropsch derived wax, petroleumderived wax, plastic, and mixtures thereof.
 31. The process of claim 29,wherein the pour point reducing blend component is selected from thegroup consisting of: a. an isomerized Fischer-Tropsch derived bottomsproduct; b. a bottoms product prepared from an isomerized highly waxymineral oil; c. an isomerized oil having a kinematic viscosity at 100°C. of at least about 8 mm²/s made from polyethylene plastic; and d.mixtures thereof.
 32. The process of claim 29, wherein the pour pointreducing blend component is prepared by: i. pyrolysis of a polyethyleneplastic; ii. separating out a heavy fraction from the pyrolysis step;iii. hydrotreating the heavy fraction; iv. catalytic isomerizing thehydrotreated heavy fraction; and v. selecting a fraction of theisomerized product having a kinematic viscosity at 100° C. of at leastabout 8 mm²/s.
 33. The process of claim 29, wherein the pour pointreducing blend component has a traction coefficient less than 0.015 whenmeasured at a kinematic viscosity of 15 mm²/s and at a slide to rollratio of 40%.
 34. The process of claim 29, wherein the two-cyclegasoline engine lubricant has a good low temperature fluidity at −25° C.35. The process of claim 29, wherein the two-cycle gasoline enginelubricant has an exhaust smoke index of greater than
 65. 36. The processof claim 29, wherein the two-cycle gasoline engine lubricant has a wt %sulfated ash of 0.18 or less.
 37. The process of claim 29, additionallycomprising blending the pour point reducing blend components with asmoke-suppression agent.
 38. The process of claim 29, wherein thedistillate base oil is Fischer-Tropsch derived.
 39. A lubricating oilmade by a process, comprising. a. hydroisomerization dewaxing asubstantially paraffinic wax feed, whereby a lubricating base oil isproduced; and b. blending one or more fractions of the lubricating baseoil with: i. less than about 5 wt % based on the total lubricating oilcomposition of a hydrocarbon solvent having a maximum boiling point lessthan 250 degrees C., and ii. a detergent/dispersant additive package;whereby the lubricating oil meets the requirements of JASO M345:2003.40. The lubricating oil made by the process of claim 39, wherein thesubstantially paraffinic wax feed is Fischer-Tropsch derived.
 41. Thelubricating oil made by the process of claim 39, wherein thehydroisomerization dewaxing uses a catalyst comprising a shape selectiveintermediate pore size molecular sieve, a noble metal hydrogenationcomponent, and a refractory oxide support.
 42. The lubricating oil madeby the process of claim 39, comprising blending the one or morefractions of the lubricating base oil with less than about 2 wt % basedon the total lubricating oil of a hydrocarbon solvent having a maximumboiling point less than 250 degrees C.
 43. The lubricating oil made bythe process of claim 39, comprising blending the one or more fractionsof the lubricating base oil with essentially no hydrocarbon solvent. 44.The lubricating oil made by the process of claim 39, additionallycomprising blending the one or more fractions of the lubricating baseoil with a smoke-suppression agent selected from the group ofpolybutene, polyisobutylene, and mixtures thereof.
 45. The lubricatingoil made by the process of claim 39, additionally comprising blendingthe one or more fractions of the lubricating base oil with a pour pointdepressant.
 46. The lubricating oil made by the process of claim 39,wherein the one or more fractions of the lubricating base oil havegreater than about 90 wt % paraffinic carbon and less than 0.01 wt %aromatic carbon by ASTM D3238-95 (2005).
 47. The lubricating oil made bythe process of claim 39, meeting the requirements of JASO M345:2003,Classification C or Classification D.
 48. The lubricating oil made bythe process of claim 39, meeting the requirements of ISO 13738:2000(E).49. The lubricating oil made by the process of claim 39, having a goodlow temperature fluidity at −25° C.
 50. The lubricating oil made by theprocess of claim 39 having a passing result in the miscibility test byASTM D4682-87(Reapproved 2002) at −10° C. or at −25° C.